Printing fluid

ABSTRACT

Aqueous, low-viscosity, printing fluids comprising an aqueous solution of (A) a thermosetting polyhydroxypolyalkylenepolyureaformaldehyde resin condensate and (B) a water-soluble dye which is compatible with the resin condensate. These printing fluids are useful in high speed paper printing processes.

United States Patent i1 1 Roccheggiani et al.

[ 1 Jan. 14, 1975 PRINTING FLUID Inventors: Guido G. Roccheggiani,Chester;

Robert W. Faessinger, Media, both of Pa.

Assignee: Scott Paper Company, Philadelphia,

Filed: Sept. 28, 1967 Appl. No.: 671,490

Related US. Application Data Continuation of Ser. No. 424,220, Jan. 8,1965, abandoned.

US. Cl -260/29.4 R, 8/7, 8/82, 8/85,117/15,117/38, 117/155, 260/70 M,260/39 P Int. Cl... C08g 51/24, C08g 51/66 Field of Search 260/29.4, 69,70; 162/126, 162/134, 162, 166, 167; 8/7, 18, 82, 85, 76; 106/20, 22;7/15, 38

References Cited Primary Examiner-John C. Bleutge Attorney, Agent, orFirmBacon and Thomas [57] ABSTRACT Aqueous, low'viscosity, printingfluids comprising an aqueous solution of (A) a thermosettingpolyhydroxypolyalkylenepolyurea-formald'ehyde resin condensate and (B) awater-soluble dye which is compatible with the resin condensate. Theseprinting fluids are useful in high speed paper printing processes.

9 Claims, No Drawings PRINTING FLUID This application is a continuationof Ser. No. 424,220, filed Jan. 8, 1965, now abandoned.

This invention pertains to novel printing fluids; more particularly,this invention relates to certain aqueous printing fluids of certainmixtures of thermosetting resins and particular dyes suitable forprinting unsized webs at printing velocities, for example, up to about5,000 ft./min. and over. The printed products obtained by printing withthe novel printing fluids are within the purview of this invention.

In a majority of prior-art rotogravure processes pigmented printingfluids of high vapor pressure solvents have been used. These fluidscontain dispersed particular matter of great hiding pow'er. Particlesdispersed within these fluids give the tinctorial strength needed forprinting when these fluids are deposited on the surface of the printedweb and the solvent removed thereafter.

While the final print quality of these fluids is often excellent, theprocess possesses inherent'limitations such as the velocity at which theweb may be printed as well as the rate of solvent removal from thepigmented fluids. Needless to say, the many dangers inherent in usinghigh vapor pressure solvents are considerable.

Other prior-art shortcomings, in comparison with this process, are thelife span of the rotogravure roll or intaglio surface because thepigmented particular materials the printing surface. This phenomenon isavoided by reducing the viscosity of the printing fluid by addingsolvent.

Therefore, it is obvious that any change in one property of the fluidwill significantly alter other properties of the fluid if the nature ofthe prior art system is signifi- I cantly changed to obtain improvedresults.

It has now been found that a completely new and unobvious approach inprinting fluids does overcome most of the prior-art shortcomings andallows the printing operations to be carried out at web velocities up toabout 5,000 ft./min. and higher or a web velocity of about a mile perminute at a cost substantially lower than achievable by any prior-artprocesses.

This printing fluid, asfurther amplified herein, is suitableforrotogravure intaglio printing of papers having an absorbency time of600 see/0.01 ml of water. Thep'referred papers have absorbencyproperties as deabrade the roll surface in places of contact with an--picted in the following table:

TABLE.

ABSORBENT PAPERS v Most More Types of Paper Preferred PreferredPreferred Multi-Ply Toilet/Facial Tissues Basis Weight lb/ream 9.2 10.77.5 ll.5 5.0 15.0 Absorbency second/0.10 ml 0 l0 0 l5 0 I Single-PlyToilet Tissue Basis Weight lb/ream l 1.5 14.0 9.0 l6.0- 7,0 20.0Absorbency sec/0.01 ml 0 6O 0 l20 O 300 Single-Ply Towel/Wiper 7 BasisWeight-lb/ream 20.0-36.0 ll.040.0 10.0-50.0 Absorbencysec./0.l0 ml 0-600360 0 6 Q0 I Multi-Ply Towel/Wiper Basis Weight-lb/ream 9.020.023.0-21.0 5.0-25.0 Absorbencysec/.0l ml 060 0-300 0-600 Single-PlyNapkin Basis Weightlb/ream 12.0- l5.5 9.0 l9.0 6.0-2.5.0Absorbencysec/0. 0l ml 0- 0'36O 0600 Multi-Ply Napkin BasisWeightlb/ream 9.7- l 1.2 7.0 15.0 5.020.0

Absorbencysec/0.10 ml other surface such as the printing nip, and doctorblades.

Basis weight is expressed in pounds per 24 X 36 inches X 480 sheet ream(2,880 square ft.).

. Absorbency is expressed in seconds as the time required for the paperspecimen to absorb a specified volume of distilled water. The area ofeach specimen (obtained from a retail case) is to be no less than 9square inches, cut to 3 X 3 inches. The specimen to be tested will besuspended in a suitable frame to provide a flat, undistorted surfacewith no contact on either side of the specimen with any other surface ormaterial. With the specimen thus prepared, the specific volume of waterin a single drop will be. lowered by appropriately divisioned pipette tothe surface of the specimen. Timing begins as the water drop touches thespecimen and ends with complete absorption defined as the instant atwhich the water on the surface fails to reflect light. For single-plytissue and/or napkins 0.01 ml H O For all others 0.10 ml H O Samplesfrom each case will be from no less than of the retail package containedtherein. Each individual test will be the result of'three drops/side,report- 'ing the 6-drop average as the individual test result. The

average of these tests will represent the absorbency.

The test described above conducted under atmospheric conditionscontrolled to 75 i 2F and 60 i 2% R.I-I.

The resin as disclosed herein is obtained by a process for preparingpolyhydroxypolyalkylenepolyureaformaldehyde condensates which comprisesreacting between about 0 and 100C, in the presence of water,epichlorohydrin and an alkylene polyamine having two to three carbonatoms in the alkylene portion thereof in a mole ratio from I 1 to 1.4 1until an aqueous solution of the resultingpolyhydroxypolyalkylenepolyaylenepolyurea with formaldehyde in asolution at a pH between 7 and 9.5. (These condensates have been furtherdescribed in- U.S. Pat. No. 2,699,435.)

In order to render the present resin acceptable for printing purposesthe resin must be modified by acidic catalysts compatible with thedye-resin solutions. Examples of such acid catalysts are such as aceticacid,

lactic acid, glycolic acid, diglycolic acid, citric acid,

phosphoric acid, hydrochloric acid, ammonium chloride, etc.

Further, to improve fluid stability, particularly at low resin-to-dye'ratios, fluid additives are included; these are exemplified by compoundssuch as formaldehyde, methyl alcohol, glyoxal, glycols such as ethylene(low molecular-weight polyethylene glycol) and propylene glycol, glycolethers such as cellosolve and Carbitol; formamide, dimethylformamide,polyvinyl pyrrolidone, tetrahydrofurfuryl alcohol, dimethyl sulfoxide,etc.

Urea is also added to the present fluid for dye solubilizing andformaldehyde scavenging. If problems exist with fluid affinity forgravure rolls, which are generally chrome plated, surface-active agentsmay be added. Examples of these are nonionic surface-active agents suchas nonylphenoxypoly(ethyleneoxide) and others obtainable from AtlasChemical Corp. such as the Atmos, Atmul, and Tween Series of non-ionics.

The resin in solution must also exhibit non-dilatant viscositycharacteristics. For purposes of this invention, the describedcondensates are also limited by the viscosity considerations as set outherein.

The water-soluble dyes useful in the novel fluid are generally thosewith anionic characteristics, i.e., bearing an opposite charge to theresin; Although the combination of a cationic resin and an anionicdyestuff is basically incompatible, this difficulty can be overcome byusing an amount of resin in excess of the stoichiometric ratio. Forexample, most water-soluble cationic thermosetting resins may be madecompatible with'direct, acid and reactive dyes.

This stabilized solution, it is believed, in turn coacts by curing onthe fibers in the web and the degree of this reaction is measured by atransference value.

As there are an untold number of dyes and each dye, it has been found,reacts unpredietably vis-a-vis the particular resin, only a certainfamily of dyes will be operative in this process. However, since theconcept of using a particular water-soluble thermosetting resin with aparticular dye is novel from the stability aspect as well as thetransfer value aspect, many dyes are eliminated on the basis of thefirst ground as well as on the second. The tests designed to delineatethe acceptable dyes from those failing in the instant fluids are set outbelow and fully discussed. Again, it is stressed that not all dyes meetthe first two requirements and that pr'e dictability is impossible toestablish beforehand. More over, in order for the dye to be acceptable,it must be used in quantities such as will establish an acceptableprint. Again, this property relates to stability as the dye affects thefluid stability if the dye is present in considerable amounts. In otherwords, for each particular resin-dye combination a direct relationshipexists between fluid stability and the ratio of resin non-volatilesolids (N.VLS.) to dye, i.e., stability is adversely affected as theresin todye ratio decreases.

Fluid stability at room temperature (77F) is herein defined as theperiod of time intercurring between the manufacture of a fluid and theappearance of physicalchemical changes that would adversely affectoperability. These changes usually take place over a period of time andthe limiting factors from the standpoint of fluid utilization are thefollowing: A i 25% change in fluid viscosity from the original value anda departure from the initial one-phase solution.

Stability is measured on an arbitrary scale defined from most preferredfluids as A, signifying astability of one month or more, for preferredfluids as B, signifying a stability of 1 week to a month, for useablefluids as C, the stability ranging from one hour to one week and forunacceptable fluids as 0, the stability being one hour or less orcomplete incompatibility in fluid components.

Fluid stability as herein defined is also indicative of shelf life orstorage life. Storage life, as defined by the Packaging Institute in theGlossary of Packaging Terms, 2nd ed., Riverside Press, Essex, Conn.,1955, is the period of time duringwhich a packaged product can be storedunder specific temperature conditions and remain suitable for use.Sometimes called shelf life.

Even if a proper amount of dye can be dissolved in the solution it maynot be acceptable because of the bleeding in water or transfer valuetest."

The novel printing fluids can also be cleaned which is hardly possiblewith the pigmented printing fluids since filtering or centrifugationwould remove pigment tinctorial material. This property of fluid givesrise to a recirculating system as, in the case of loosely-bondedabsorbent papers, the paper dust and loose fibers must be removed fromthe fluid in order not to overload the system with particulatematerials. Therefore, the need for a low-viscosity aqueous solution isimportant as these solutions can be easily cleaned or separated fromimpurities such as by'centrifugation. This viscosity criterion is ofimportance because the impurities are removed by cleaning means such asthose based upon differences in specific gravity. Consequently,dust-laden webs as well as loosely-bonded webs can be printed by meansof this fluid because they are cleanable.

Transference, as previously mentioned, relates to the ability of theprinted area to resist water washing or bleeding after the resin hascured to the thermosetting state. i

Transference solutions establishing the standard values for thedifferent resin dye mixtures and classifying acceptable fluids are givenbelow:

Transfer is herein defined as the amount of tinctorial material removedfrom the original colored area by the addition of distilled water andtransferred to either an unprinted area of the same substrate or ontoanother substrate when physical contact is established.

Transfer rating scale:

No noticeable transfer 1 Very slight (barely noticeable) transfer 2Slight transfer 3 Moderate transfer 4 Heavy transfer 5 Very heavytransfer The transfer rating scale is based on the intensity of thecolor removed when compared with the intensity of the original coloredarea.

Transfer rating is by definition 0 as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue I dyestuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml ofdistilled water heatedto 130F and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30% N.V.S.),U.S. Pat. No. 2,699,435 (Example 2, appro priately adjusted for itsN.V.S. content) Uformite 700 (Rohm & Haas) with agitation. Subsequently,3 g. of NH Cl are added to the dye-resin solution and mixing iscontinued-until the catalyst is completely dissolved. Using a 100microliter pipette, three-hundredths of one ml (0.3 ml) of fluid isplaced on a No. l Whatmanfilter paper and dried (cured) for 1 hour in anoven at 230F. Thecolored portion of the filter'paper is then immersedfor 5 seconds in distilled water, the excess water is removed bycontacting any absorbent medium, and finally the damp test sample issandwiched between two two-layer pads of No. l Whatman filter paper. Atwo-pound weight is placed on the top of the filter pad and remainsthere for at least hours, after which time the sample is removed and the2 filter surfaces in 7 a 100 microliter pipette, three-hundredths of 1ml (.03

ml) of fluid is placed on a No. 1 Whatman filter paper and dried (cured)for 10 minutes in an oven at 230F. The colored portion of the filterpaper is then immersed for five seconds in distilled water, the excesswater is removed by contacting any absorbent medium, and finally thedamp test sample is sandwiched between two two-layer pads of No. lWhatman filter paper. A 2-pound weightis placed on the top of the filterpad and remains there for'at least 10 hours after which time the sampleis removed and the two filter surfaces in contact with the test,sampleupon examination exhibit a very slight (barely noticeable)transfer.

Transfer ratingis by definition 2 as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue 1 dyestuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml of distilled waterheated to [30F and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30% N.V.S.)U.S. Pat. No. 2,699,435, Uformite 700 (Rohm & Haas) with agitation.Subsequently, 0.5 g. of NH CI is added to the dye-resin solution andmixing is continued until the catalyst is completely dissolved. Using amicroliter pipette, three-hundredths of 1 ml (.03 ml) of fluid is placedon a No. l Whatman filter paper and dried (cured) for 60 minutes in anoven at 230F. The colored portion of the filter paper is then immersedfor 5 seconds in distilled water, the excess water is removed bycontacting any absorbent medium, and finally the damp test sample issandwiched between two two-layer pads of No. 1 Whatman filter paper. A2-pound weight is placed on the top of the filter pad and remains therefor at least 10 hours, after which time the sample is removed and thetwo filter surfaces in contact with the test sample upon examinationexhibit a-slight transfer.

Transfer rating is by definition 3 as a result of carry-' ing out thefollowing experiment: 2 g. of C.I. Direct Blue 1 dyestuff (DuPontPontamine Sky Blue BX) are dissolved in 50 ml of distilled water heatedto F and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30% N.V.S.),U.S. Pat. No. 2,699,435, Uformite 700 (Rohm & Haas) with agitation.Subsequently, 0.5g. of NH Cl is added to the dye-resin solution andmixing is continued until the catalyst is completely'dissolved. Using a100 microliter pipette, three-hundredths of one ml (0.3 ml) of fluid isplaced on a No. 1 Whatman filter paper and dried (cured) for 30 minutesin an oven at 230F. The colored portion of the filter paper is thenimmersed for 5 seconds in distilled water, the excess water is removedby contacting any absorbent medium,

and finally the damp test sample is sandwiched between two two-layerpads of No. 1 Whatman filter paper. A 2-pound weight is placed on top ofthe filter pad and remains there for at least ten hours, after whichtime the sample is removed and the two filter surfaces in contact withthe test sample upon examination exhibit a moderate transfer.

Transfer rating is by definition 4 as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue l dyestuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml of distilled waterheated to 130F and transferred into 50 g. of polyhydroxypolyalkdamp testsample is sandwiched between two two-layer pads of No. l Whatman filterpaper. A 2-pound weight is placed on the top of the filter pad andremains there for-at least 10 hours, after which time the sample isremoved and the two filter surfaces in contact with the test sample uponexamination exhibit a heavy transfer.

Transfer rating is by definition 5 as a result of carrying out thefollowing experiment: 2 g. of C.I. Direct Blue 1 dyestuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml of distilled waterheated to 130F andtransferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30% N.V.S.),U.S. Pat. No. 2,699,435 Uformite 700 (Rohm & Haas) with agitation.Subsequently, the dye-resin solution pH is adjusted to by addition of 20drops of saturated NaOH solution and mixed until the catalysthigh-surface tension values because low viscosity fluid wets theintaglio surface at acceptable rates. Depending on the degree of surfacewetting the surface tension may be varied by adding minor amounts ofwetting agents to give the best results. The preferred values are below50 dynes/cm and below the surface value of pure water (72 dynes/cm). Anacceptable range is of fromabout 30 dynes/cm to about 60 dynes/cm. Thesurface tension is measured by means of Cenco-duNouy tensiis completelydissolved. Using a 100 microliter pipette,

ometer.

In comparing the print obtained by means of the prior art pigmentedrotogravure inks with the print obtained by the novel fluid thefollowing differences exist. The prior art inks are opaque, i.e., theyhave considerable hiding power (impervious to the rays of light). On theother hand, the present dyes are transparent although these may becolored. The color value adjustment in prior art is obtained by addingwhite pigment wiched between two two-layer pads of No. l Whatman filterpaper. A 2-pound weight is placed on the top of the filter pad andremains there for at least 10 hours,

after which time the sample is removed and the two fil-' ter surfaces incontact with the test sample upon examination exhibit a very heavytransfer.

For the process to be operative at the high-web velocities such as above5,000 ft./min. the viscosity of the fluid must be kept within certainlimits. At lower web velocities the viscosity may be higher such asabout 20 cps, but again, a more viscous fluid picks up more fiber andmay be harder to clean and for this reason is not desirable. Forpurposes of this process viscosities below cps are preferred. Thepreferred range of viscosity for the fluid is offrom about 3 cps to 10cps while the most preferred range is about 3 cps to about 7 cps at 77F.

In the instant case procedure for determination of liquid viscosities bythe Cannon-Fenske Routine Viscometer was used. Equipment needed forviscosity determination includes a constant temperature bath, a timerand the proper size Cannon-Fenske Routine Viscometer tube. Size 50 tubeis recommended for a range of 0.8 to 3.2 centistokes, size 100 tube for3 to 12 centistokes, size 150 tube for 7 to 28 centistokes and size 200tube for to 80 centistokes.

The bath temperature is maintained at 250C i 01C. The viscosity incentipoises is-then calculated by multiplying the centistoke viscosityby the liquid density at C. The liquid density at 25C is calculated bythe following equation: Density of liquid at 25C (sp.g. at tF) (dens.water at 60F) Dons. water at. 25 C.

dens. water at l I*.

(s1). ,2. tF.) (dons. water at t F.)

and coloring. In the present fluids it is performed by preparing adifferentfluid with a different dye concentration. In practicing thisinvention, the white pigment is not needed and its place is taken by thecolor of the substrate, i.e., the color of fibers which are for the mostpart white for bleached pulp. Consequently a component previouslyrequired in a rotogravure ink is now eliminated. Of e o ursefthieprinting of colored base sheets necessitates the use of colors that,upon becoming deposited on the base sheets will give the needed color,e.g., a blue base sheet must be printed with yellow dye-resin solutionto obtain green color.

Besides the above factors which contribute to the acceptance of thepresent fluids, the cost factor is an equally important considerationherein. For example, the cost as well as the necessity of pigment andgrinding of it is eliminated because no pigment is used in this process.Reproducibility of color is extremely good because of standardized dyesand standardized colors.

Uniformity of fluid concentration is easily maintained even during verylong runs as no large amounts of vola-,

tile solvents are used which require constant adjustment. Needless tosay, these advantages render the present fluid much less costly andespecially suitable for modern mass production methods.

The following examples will serve further to illustrate the invention:

EXAMPLE 1 50 parts by weight of urea were dissolved in 450 parts waterin a stainless steel tank equipped with an agitator and means forheating. 40 parts by weight of a direct dye, Pontamine Brilliant GreenGX, DuPont which is a mechanical mixture of the following two directdyes: 86% Pontamine Fast Yellow 4GL, C.I. (Color Index) Direct Yellow44, 14% Pontamine Sky Blue 6BX, C.I. Direct Blue 1, were dissolved inthe urea solution, with agitation and heating to approximately 140F. Theresulting solution was added slowly, with agitation, to a second vesselcontaining 500 parts by weight'of aqueous, cationicpolyhydroxypolyalkylenepolyureaformaldehyde resin solution of the typedescribed in U.S. Pat. 2,699,435 (Uformite 700, Rohm & Haas) having anN.V.S. concentration of approximately 30%. The resulting solution wasagitated for 15 minutes and 8.8 parts by weight of Phosphoric Acidcatalyst were slowly added. After an additional 10 minutes mixing 1 partby weight of surfactant Igepal C0 630, General Aniline, a active liquidnonionic surfactant, i.e., nonylphenoxypoly(ethylene oxide) was slowlyadded.

The fluid-had the following properties: pH 7.2,

N.V.S. 29.5%, specific gravity 1.119 at 77F, viscos- I crepe paper,i.e., facial tissue, by commercial direct rotogravure at speeds up to2900 fpm. The paper was cut and folded into facial tissue form, havingan attractive green design imprinted thereon, which print had a colortransfer rating of 1 after 4 weeks of aging at room temperature. (Theeffectiveness of cure by aging is generally measured by water solubilityof the resin and determined at room temperature conditions).

EXAMPLE 2 50 parts by weight of urea were dissolved in 450 parts waterin a stainless steel tank equipped with an agitator and means forheating. 13.4 parts by weight of a reactive dye, Cibacron Brilliant BlueBRP, C.I. Reactive Blue 5, and 6.6 parts by weight of a reactive dye,Cibacron Turquoise Blue G-E, C.I. Reactive Blue 1, Ciba, were dissolvedin the urea solution, with agitation and heating to approximately 140F.The resulting solution was added slowly, with agitation to a secondvessel containing 500 parts by weight ofpolyhydroxypolyethylenepolyurea-formaldehyde resin (Uformite 7'00, Rohm& Haas) having an N.V.S. concentration of approximately 30%.' Theresulting solution was agitated for minutes and 8.8 parts by weight of75% Phosphoric Acid catalyst was slowly added. After an additional 10minutesl part by weight of surfactant lgepal CO 630 (General Aniline)was slowly added.

The fluid had the following properties: pH 6.9, N.V.S. 29.1%, specificgravity 1.100, viscosity 3.98 cps, surface tension 32.9 dy-nes/cm.,stability 2 months. Y

Just prior to use, 7.5 parts of perfume oil (Bouquet L-P-3580-8, PerryBros., Inc.) were slowly added with agitation.

The fluid was printed on soft, absorbent two-ply dry crepe paper,i.e.,-toilet tissue, by commercial direct rophoric Acid catalyst wasslowly added. After an additional 10 minutes mixing 1 part by weight ofsurfactant lgepal CO 630, General Aniline, was slowly added.

The fluid had the following properties: pH 7.0, N.V.S. 24.9%, specificgravity- 1.101, viscosity 3.32 cps, surface tension 31.8 dynes/cm,stability 49 days.

Just prior to use, 7.5 parts of perfume oil (Bouquet LP35808, PerryBros., Inc.) was slowly added with agitation. I

The fluid was printed on soft, absorbent two-ply dry crepe paper, i.e.,facial tissue, by commercial direct rotogravure at speeds up to 2900fpm. The paper was cut and folded into facial tissue form, having anattractive pink design imprinted thereon, which print had a colortransfer rating of 0 after-4 weeks of aging at room temperature.

EXAMPLE 4 41.66 parts by weight of urea were dissolved in 291.65 partswater in a stainless steel tank equipped Y with an agitator and meansfor heating. 21.99 parts by tog'ravure at speeds up to 2900 fpm. Thepaper was cut and rolled into toilet tissue form, having an attractiveblue design imprinted thereon, which print had a color transfer ratingof 0 after 4 weeks of aging at room temperature.

EXAMPLE 3 parts by weight of urea were dissolved in 450 parts water in astainless steel tank equipped with an agitator and means for heating.19.4 parts by weight of a reactive dye, Drimarine Scarlet Z-GL P.A.F.,C.I. Reactive Red 19, Sandoz, and .6 part by weight ofa reactive dye,Drimarine Red Z-2B P.A.F., C.l. Reactive Red 17, Sandoz, were dissolvedin the urea solution, with agitation and heating to approximately 140F.The resulting solution was added slowly, with agitation to a secondvessel containing 500 parts by weight ofpolyhydroxypolyalkylenepolyurea-formaldehyde resin (Uformite 700, Rohm &Haas) having an N.V.S. concentration of approximately 30%. The resultingsolution was agitated for 15 minutes and 8.8 parts by weight of 75%Phosweightof a direct dye, Pontamine Fast Yellow RL', C.I. Direct Yellow50, DuPont, and 2.99 parts by weight of a direct dye, Pontamine FastBrown NP, C.I. Direct Brown 95, DuPont, were dissolved in the ureasolution, with agitation and heating to approximately 140F. Theresulting solution was added slowly, with agitation to a second vesselcontaining 500 parts by weight ofpolyhydroxypolyalkylenepolyure'a-formaldehyde resin (Uformite 700, Rohm& Haas) having an N.V.S. concentration of approximately 30%. Theresulting solution was agitated for 15 minutes and 8.33 parts by weightof Phosphoric Acid catalyst was slowly added. After an additional 10minutesmixing -.83 part by weight of surfactant lgepal CO 630, GeneralAniline, was slowly added.

The fluid had the following properties: pH 7.4, N.V.S. 26.9%, specificgravity 1.124, viscosity 5.83 cps, surface tension 32.8 dynes/cm.,stability L 67 days.

Just prior to use 6.25 parts of perfume oil (Bouquet LP-3580-8, PerryBros, Inc.) was slowly added with agitation.

The fluid was printed on soft, absorbent two-ply dry crepe paper, i.e.,facial tissue, by direct rotogravure at speeds up to 2900 fpm. The'paperwas cut and rolled ing of 1 after 4 weeks of aging at room temperature.

EXAMPLE 5 In parts water, 6 parts by weight of the direct dye, PontamineBrilliant Green GX, were .dissolved with agitation and heating toapproximately F. The resulting solution was added slowly, with agitationto a second vessel containing 100 parts by weight ofpolyhydroxypolyalkylenepolyurea-formaldehyde resin (Uformite 700,'Rohm &Haas) having an N.V.S. content of approximately 30%. The resultingsolution was agitated for 10 minutes and 2 parts NH CI catalyst wereslowly added.

The fluid had the following properties: pH 6.6, N.V.S. 17.7%, specificgravity 1.082, viscosity 3.05 cps, surface tension 48.0 dynes/cm.,stability 149 days.

The fluid was printed with a 19 inch wide commercial rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent two-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive greendesign imprinted thereon, which print had a color transfer rating of 2after 4 weeks of aging at room temperature.

EXAMPLE 6 The fluid had the following properties: pH- 6.4,

N.V.S. 18.5%, specific gravity 1.084, viscosity 3.74 cps, surfacetension l.6 dynes/cm., stability 140 days. I

The fluid was printed with a 19 inch wide commercial rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent two-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive reddesign imprinted thereon, which print had a color transfer rating of 0after 4 weeks of aging at room temperature.

EXAMPLE 7 In 100 parts water, 3.33 parts by weight of the reactive dye,Cibacron Brilliant Blue BR, C.l. Reactive Blue 5, Ciba, and 0.67 partsby weight of the reactive dye, Cibacron Turquoise Blue G, C.l. ReactiveBlue 7, Ciba, were dissolved with agitation and heating to approximately140F. The resulting solution was added slowly, with agitation to asecond vessel containing 100 parts by weight I ofpolyhydroxypolyalkylenepolyureaformaldehyde resin (Uformite 700, Rohm &Haas) having an N.V.S. of approximately 30%. The resulting solution wasagitated for 10 minutes and 2 parts of NH Cl catalyst was slowly added.

The'fluid had .the following properties: pH 6.4, N.V.S. 17.4%, specificgravity 1.076, viscosity 2.83 cps, surface tension 39.1 dynes/cm.,stability 90 days.

The fluid was printed with a 19 inch wide commercial rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent two-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive bluedesign imprinted thereon, which print had a color transfer rating of 0after 4 weeks aging at room temperature.

EXAMPLE 8 In 100 parts water, 5.0 parts by weight of the direct dye,PontamineFast Yellow RL, C.l. Direct Yellow 50,

sulting solution was agitated for 10 minutes and 2 parts of NH CIcatalyst were slowly added.

The fluid had the following properties: pH 6.7, N.V.S. 18.6%, specificgravity 1.087, viscosity 3.49

cps, surface tension 47.7 dynes/cm., stability 92 EXAMPLE 9 In 100 partswater, 5.88 parts by weight of the acid dye, Lanasy Brilliant Blue GL,C.l. Acid Blue 127, Sandoz, and 0.6 part by weight of the direct dye,ErieBrilliant Violet B Conc. (200%), C.l. Direct Violet 9, AlliedChemical, 0.6 part by weight of the direct dye, Pontamine Black ETP,C.l. Direct Black 38, DuPont, were dissolved with agitation and heatingto approximately 140F. The resulting solution was added slowly, withagitation to a second vessel containing 100 parts by weight ofpolyhydroxypolyalkylenepolyureaformaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. of approximately 30%. The resultingsolution was agitated for 10 minutes and 2 parts of NH Cl catalyst wasslowly added.

The fluid had the following properties: pH 6.4, N.V.S. 19.4%, specificgravity 1.088, viscosity 4.67 cps, surface tension 34.4 dynes/cm.,stability 90 days.

The fluid was printed with a 19 inch wide commercial rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent two-ply drycrepe tissue, i.e, facial tissue. The paper had an attractive bluedesign imprinted thereon, which print had a color transfer rating of 2after 4 weeks of aging.

EXAMPLE 10 In 100 parts water, 4 parts by weight of the direct dye,Pontamine Fast Scarlet 4BA, C.l. Direct Red 24, DuPont, were dissolvedwith agitation and heating to approximately 140F. The resulting solutionwas added slowly, with agitation to a second vessel containing 100 partsby weight of polyhydroxypolyalkylenepolyureaformaldehyde condensate(Uformite 700, Rohm &

Haas) having and N.V.S. of approximately 30%. The

resulting solution was agitated for 10 minutes and 2 V N.V.S. 18.3%,specific gravity 1.086, viscosity 3.90

cps, surface tension 44.2 days.

The fluid was printed with a 19 inch wide commercial rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent two-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive reddesign imprinted thereon, which print had a color transfer rating of 2after 4 weeks of aging.

EXAMPLE 1 1 10 parts by weight of urea were dissolved in parts water. 3parts by weight of the direct dye, Fiber Black VF, C.l. Direct Black 38,Dupont, were dissolved in the above solution with agitation and heatingto approximately F. The resulting solution was added slowly,

dynes/cm., stability 90 with agitation to a second vessel containing 100parts by weight of polyhydroxypolyalkylenepolyureaformaldehydecondensate (Uformite 700, Rohm & Haas) having an N.V.S..of approximately30%. The resulting solution was agitated for minutes and 2.50 parts of75% Phosphoric Acid catalyst and 4.0 parts of surfactant lgepal CO 630,General Aniline, were slowly added.

The fluid had the following properties: pH 6.8, stability 68 days.

The fluid was printed at 300 fpm on a inch wide laboratory rotogravureprinting unit on soft, absorbent two-plywet crepe tissue, i.e., napkinbase stock. The paper hadan attractive black design imprinted thereon,which print had a colortransfer rating of 1 after 4 weeks of aging.

EXAMPLE 12 100 parts by weight of urea were dissolved in 400 partswater. 19.4 parts by weight of the reactive dye, Drimarine Scarlet ZGL,C.I. Reactive Red 19, Sandoz, and 0.6 parts by weight of the reactivedye, Drimariune Red 228, Sandoz, were dissolved in the above solutionwith agitation and heating to approximately 140F. The resulting solutionwas added slowly, with agitation to a second vessel containing 500 partsby weight of polyhy-. droxypolyalkylenepolyurea-forrnaldehyde resin(Uformite 700, Rohm & Haas) having an N.V.S. content of approximately30%. The resulting solution was agitated for 1 hour and 10 parts NH Clcatalyst was slowly added. When mixed, 2 parts or surfactant, PluronicL64, Wyandotte, and 7.5 parts perfume oil (Bouquet LP3580-8, Perry Bros,Inc.) were added.

The fluid had the following properties: pH 6.4,

N.V.S. 27.5%, specific gravity 1.116, viscosity 4.83 cps, surfacetension 35.7 dynes/cm., stability 43 days.

The fluid was printed at 300 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent two-ply dry crepe tissue,i.e., table napkin base stock. The paper was embossed, cut and foldedinto napkins having an attractive pink design imprinted thereon, whichprint had a color transfer rating of Oafter 4 weeks of aging.

EXAMPLE 13 I 100 parts by weight of urea were dissolved in 90 partswater. 3 parts by weight of the direct dye, Solophenyl Turquoise BlueGTL Extra, C.I. Direct Blue 86, Geigy, were dissolved in the abovesolution with agitation and heating to approximately 140F. The resultingsolution was added slowly, with agitation to a second vessel containing100 parts by weight of polyhydroxypolyalkylenepolyurea formaldehydecondensate (Uformite 700, Rohm & Haas). The resulting solution wasagitated for 10 minutes and 2.5 parts 75% Phosphoric Acid catalyst and0.4 parts of surfactant lgepal CO 630, General Aniline, were slowlyadded.

The fluid had the following properties: pH 6.5, stability 68 days.

EXAMPLE 14 10 parts by weight of urea were dissolved in 90 parts water.2.25 parts by'weight of the direct dye, Berkshire Direct Fast Scarlet 4GS, C.I. Direct Red 24, and 0.75 parts by weight of the direct dye,Berkshire Bond yellow CG, were dissolved in the above solution withagitation and heating to approximately 140F. The resulting solution wasadded slowly, with agitation to a second vessel containing 100 parts byweight of polyhydroxypolyalkylenepolyurea-formaldehyde condensate(Uformite 700, Rohm & Haas) with an N.V.S. of approximately 30%.The'resulting solution was agitated for 10 minutes and 2.5 parts 75%Phosphoric Acid catalyst and 0.4 parts of surfactant lgepal CO 630,General Aniline, were slowly added.

The fluid had the following properties: pH 6.7, stability 42 days.

The fluid was printed at 300 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent two-ply wet crepe tissue,i.e., napkin base stock. The paper had an attractive reddish-yellowdesign imprinted thereon, which print had'a color transfer rating of 0after 4 weeks of aging.

EXAMPLE 15 10 parts by weight of urea were dissolved in 90 parts water.2.25 parts by weight of the direct dye, Diphenyl GoldenYellow RP, Geigy,and 075 parts by weight of bility 49 days.

The fluid was printed at 300 fpm on a 15 inch wide The fluid was printedat 300 fpm on a 15 inch wide laboratory rotogravure printing unit onsoft, absorbent two-ply wet crepe tissue, i.e., napkin base stock. Thepaper had an attractive yellowish-brown design imprinted thereon, whichprint had a color transfer rating 7 of 1 after 4 weeks of aging.

EXAMPLE 16 10 parts by weight of urea were dissolved in parts water. 3parts by weight of the direct dye, Solophenyl Turquoise Blue GTL Extra,C.I. Direct Blue 86, Geigy, were dissolved in the above solution withagitation and heating to approximately 140F. The resulting solution wasadded slowly, with agitation to a second vessel containing parts byweight of polyhydroxypolyalkylen e-polyurea-fo rmaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. of approximately 30%. Theresulting solution wasagitated for 10 minutes and 2.5 parts of 75%Phosphoric Acid catalyst and 0.4 parts of lgepal CO 630, GeneralAniline, were slowly added.

The fluid had the following properties: pH 6.5, stability 68 .days.

The fluid was printed at 300 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, one-ply sized wet crepe tissue; basisweight 20.6 lbs/ream, made on an experimental paper machine. The paperhad a turquoise design imprinted thereon, which print had a colortransfer rating'of after 4 weeks of aging.

EXAMPLE 17 parts by weight of urea were dissolved in 90 parts water. 3parts by weight of the direct dye, Solophenyl Turquoise Blue GTL Extra,C.l. Direct Blue 86, Geigy, were dissolved in the above solution withagitation and heating to approximately 140F'. The resulting solution wasadded slowly, with agitation to a second vessel containing 100 parts byweight of polyhydroxypolyalkylenepolyurea-formaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. of approximately 30%. Theresulting solution was agitated for 10 minutes and 2.5 parts 75% H POcatalyst and 0.4 parts of lgepal CO 630, General Aniline, were slowlyadded.

The fluid had the following properties: pH 6.5, stability 28 days.

The fluid was printed at 300 fpm on a inch wide laboratory rotogravureprinting unit on soft, absorbent one-ply unsized wet crepe tissue, basisweight 20.6 lbs/ream. The paper had an attractive turquoise designimprinted thereon, which print had a color transfer rating of 0 after 4weeks of aging.

EXAMPLE 18 10 parts by weight of urea were dissolved in 90 parts water.3 parts by weight of the direct dye, Solophenyl Turquoise Blue GTLExtra, C.I. Direct Blue 86, Geigy, were dissolved in the above solutionwith agitation and heating to approximately 140F. The resulting solutionwas added slowly, with agitation to a second vessel containing 100 partsby weight of polyhydroxypolyalkylenepolyurea-formaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. of 30%. The resultingsolution was agitated for 10 minutes and parts of 75% H PO catalyst and0.4 parts by weight of lgepal CO 630, General Aniline, were slowlyadded.

The fluid had the following properties: pH 6.5, stability 68 days.

The fluid was printed at 300 fpm on a 15 inch wide laboratoryrotogravure printing unit on one-ply bond paper, i.e., basis weight 36.4lbs/ream. The paper had an attractive turquoise design imprintedthereon, which print had a color transfer rating of 0 after 4 weeks ofaging.

EXAMPLE 19 6 parts by weight of urea were dissolved in 94 parts water.4.0 parts by weight of the direct dye, Durafast Orange 4 GLL, C.I.Direct Orange 72, Berkshire, and 1.0 parts by weight of the direct dye,Pontamine Fast Brown NP, C.I. Direct Brown 95, were dissolved in theabove solution with agitation and heating to approximately 140F. Theresulting solution was added slowly, with agitation to a second vesselcontaining 100 parts by weight ofpolyhydroxypolyalkylenepolyureaformaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. of approximately The resulting solutionwas agitated for 10 minutes and 1.76 parts of 75% Phosphoric Acidcatalyst and 0.4 parts surfactant lgepal CO 630, General Aniline, wasslowly added.

The fluid had the following properties: pH 6.75, stability 29 days.

The fluid was printed at 300 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent two-ply dry crepe tissue,i.e., facial type.'The paper had an attractive golden yellow designimprinted thereon, which print had a color transfer rating of 2 after 2weeks of aging.

EXAMPLE 20 6 parts by weight of urea were dissolved in 94 parts water.2.8 parts by weight of the direct dye, Solophenyl Turquoise Blue GTLExtra, C.l. Direct Blue 86, Geigy, and 1.2 parts by weight of the directdye, Direct Brilliant Blue P-5BC, C. 1. Direct Blue 25, Ciba, weredissolved in the above solution with agitation and heating toapproximately 140F. The resulting solution was added slowly, withagitation to a second vessel containing 100 parts by weight ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (Uformite 700,Rohm & Haas). The resulting solution was agitated for 10 minutes and1.76 parts l l PO catalyst and 0.2% lgepal CO 630, General Aniline, wereslowly added. I

The fluid had the following properties: pH 7.0, stability 34 days.

The fluid was printed at 300 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent two-ply dry crepe tissue,i.e., facial tissue. The paper had an attractive blue design imprintedthereon, which print had a color transfer rating of 2 after 4 weeks ofaging.

EXAMPLE 21 solution was agitated for 10 minutes and 2.5 parts by weightof 75% Phosphoric Acid catalyst were slowly added. After an additional10 minutes of mixing, 0.4

parts by weight of surfactant lgepal CO 630, General Aniline, wereslowly added.

The fluid had the following properties: pH 7.5, stability 117 days.

The fluid was applied by hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a rating of 1 after 4 weeks of aging.

EXAMPLE 22 10 parts by weight of urea were added to parts of water in acontainer equipped with an agitator and means for heating. 4 parts byweight of a direct dye,

Pontamine Fast Yellow RL, C.1. Direct Yellow 50, Du- Pont, and weredissolved in the urea-water solution, with agitation and heating to140F. The resulting solution was added slowly with agitation to parts byweight of polyhydroxypolyalkylenepolyureaformaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. content of approximately30%. The resulting solution was agitated for 10 minutes and 2.5 parts byweight of 75% Phosphoric Acid catalyst were slowly added. After anadditional 10 minutes of mixing, 0.4 part by weight of surfactant IgepalCO 630, General Aniline, was slowly added.

The fluid had the following properties: pH 7.5, stability 117 days. aThe fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 2 after 4 weeks of aging.

EXAMPLE 23 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 6 parts byweight of a direct dye, Pontamine Fast yellow RL, C'.I. Direct Yellow50, Du- Pont, were dissolved in the urea-water solution, with agitationand heating to 140F. The resulting solution was added slowly withagitation to 100 parts by weight of condensate (Uformite 700, Rohm &Haas) having an N..V.S. content of approximately 30%. The resultingsolution was agitated forv 10 minutes and 2.5 parts by weight of 75%Phosphoric Acid catalyst were slowly added. After an additional 10minutes of mixing, 0.4 part by weight of surfactant Igepal CO 630,General Aniline, was slowly added.

The fluid had the following properties: pH 7.6, stability l l days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry polyhydroxypolyalkylenepolyurea-formaldehydecrepe paper, i.e., facial tissue. The yellow imprinted area had atransfer rating of 3 after 4 weeks of aging.

EXAMPLE 24 2 parts by weight of a direct dye, Pontamine Fast Scarlet4BA, C.I. Direct Red 24, Dupont, were added to 100 parts of water in acontainer equipped with an agitator and heating to 140F. The resultingsolution was added slowly with agitation to 100 parts by weight ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. content of approximately 30%. Theresulting solution was agitated for 10 minutes and 4 parts by weight ofammonium chloride catalyst were slowly added.

The fluid had the following properties: pH 6.4, stability days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 0 after 4 weeks of aging.

EXAMPLE 25 4 parts by weight of a direct dye,.Berkshire Direct FastScarlet 4BKA, C.I. Direct Red 24, were added to 100 parts of water in acontainer equipped with an agitator and heating to 140F. The resultingsolution was added slowly with agitation to 100 parts by weight ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. content of approximately 30%. Theresulting solution was agitated for 10 minutes and 2 parts by weight ofNH Cl catalyst were slowly added.

The fluid had the following properties: pH 6.1, stability 62 days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 1 after 4 weeks. of aging.

EXAMPLE 26 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 4 parts byweight of a direct dye, Solophenyl Turquoise Blue GTL, Extra, C.I.Direct Blue 86, Geigy, were dissolved in the ureawater solution, withagitation and heating to 140F. The resulting solution was added slowlywith agitation to 100 parts by weight ofpolyhydroxypolyalkylenepolyureaformaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. content of approximately 3.0%. Theresulting solution was agitated for 10 minutes and 2 parts by weight ofPhosphoric Acid catalyst were slowly added. After an additional 5minutes of mixing, 0.4 parts by weight of surfactant Igepal CO 630,General Aniline, were slowly added.

The fluid had the following properties: pH 6.8, stability 47 .days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. Theturquoise imprinted area had a transfer rating of 1 after 4 weeks ofaging.

EXAMPLE 27 10 parts by weight of urea were added to parts of water in acontainer equipped with an agitator and means for heating. 6 parts byweight of a direct dye, Solophenyl Turquoise Blue GTL Extra, C.I. DirectBlue 86, Geigy, were dissolved in the aqueous urea'solution, withagitation and heating to 140F. The resulting solution was added slowlywith agitation to parts by weight ofpolyhydroxypolyalkylenepolyureaformaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. content of approximately 30%. Theresulting solution was agitated for 10 minutes and 2 parts by weight of75% Phosphoric Acid catalyst were slowly added. After an additional 5minutes of mixing, 0.4 parts by weight of surfactant lgepal CO 630,General-Aniline, were slowly added. 7

The fluid had the following properties: pH 6.8, stability 47 days. 7

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. Theturquoise imprinted area had a transfer rating of 2 after 4 weeks ofaging.

EXAMPLE 28 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 4 parts byweight of a direct dye, DuPont Fiber Black VF, C.I. Direct Black 38,were dis solved in theurea-water solution, with agitation and heating toF. The resulting solution was added slowly with agitation to 100 partsby weight of polyhydroxypolyalkylenepolyurea-formaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. content of approximately30%. The'resulting solution was agitated for 10 minutes and 2 parts byweight of 75% Phosphoric Acid catalyst were slowly added. After anadditional 10 minutes of mixing, 0.4 part by weight of surfactant lgepalCO 630, General Aniline, were slowly 7 The fluid was applied by ahand-operated simulated rotogravure method on soft, absorbent two-plydry crepe paper, i.e., facial tissue. The black imprinted area had atransfer rating of 1 after 4 weeks of aging.

EXAMPLE 29 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 3 parts byweight of a direct dye, Golden Yellow RP, Geigy, and 1 part by weight ofa direct dye, Pontamine Brown N3G, C.l. Direct Brown 154, were dissolvedin the urea-water solution, with agitation and heating to 140F. Theresulting solution was added slowly with agitation to 100 parts byweight of polyhydroxypolyalkylenepolyurea-formaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. content of approximately30%. The resulting solution was agitated for 10 minutes and 2 parts byweight of 75% Phosphoric Acid catalyst were slowly added. After anadditional 10 minutes of mixing, 0.4 part by weight of surfactant IgepalCO 630, General Aniline, was slowly added.

The fluid had the following properties: pH 7.3, stability 77 days.

The fluid was applied by a hand operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. Thebrownish-yellow imprinted area has a transfer rating of 3 after 4 weeksof aging.

EXAMPLE 30 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 4 parts byweightof a reactive dye, Reactone Turquoise Blue FGL, C.I. Reactive Blue18, Geigy, were dissolved in the urea-water solution, with agitation andheating to 140F. The resulting solution was added slowly with agitationto 100 parts by weight of polyhydroxypolyalkylenepolyurea-formaldehydecondensate (Uformite 700, Rohm & Haas) having an N.V.S. content ofapproximately 30%. The resulting solution was agitated for 10 minutesand 2.5 parts by weight of 75% Phosphoric Acid catalyst were slowlyadded. After an additional 5 minutes of mixing, 04 part by weight ofsurfactant Igepal CO 630, General Aniline, was slowly added.

The fluid had the following properties: pH 7.0, stability 77 days.

The fluid was applied by a hand operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. Theturquoise imprinted area had a transfer rating of 0 after 4 weeks ofaging.

EXAMPLE 31 parts by weight of urea were added to 90 parts of water in acontainer equipped with an agitator and means for heating. 4 parts byweight of an acid dye, Brilliant Acid Blue G2L, Geigy, were dissolved inthe urea-water solution, with agitation and heating to 140F. Theresulting solution was added slowly with agitation to 100 parts byweight of polyhydroxypolyalkylenepoly-urea-formaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. content of approximately30%. The resulting solution was agitated for 10 minutes and 2.50 partsby weight of 75% Phosphoric Acid catalyst were slowly added. After anadditional 10 minutes of mixing, 0.4 parts by weight of surfactantIgepal CO 630, General Aniline, were slowly added. The fluid had thefollowing properties: pH 6.6, stability 25 days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The lightblue imprinted area had a transfer rating of 2 after 4 weeks of aging.

EXAMPLE 32 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 4 parts byweight of a reactive dye, Procion yellow 4RD, I.C.l., were dissolved inthe ureawater solution, with agitation and heating to 140F. Theresulting solution was added slowly with agitation to 100 parts by-weight of polyhydroxypolyalkylenepolyurea-formaldehyde condensate(Uformite 700, Rohm & Haas) having an N.V.S. content of approximately30%. The resulting solution was agitated for 10 minutes and 2.50 partsby weight of Phosphoric Acid catalyst were slowly added. After anaddition 5 minutes of mixing, 0.4 parts by weight of surfactant IgepalCO 630, General Aniline, were slowly added.

The fluid had the following properties: pH 6.6, stability 75 days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 3 after 4 weeks ofaging.

EXAMPLE 33 10 parts by weight of urea were added to parts of water in acontainer equipped with an agitator and means for heating. 4 parts byweight of an acid dye, Metanil Yellow P Conc., C. 1. Acid Yellow 36,Allied Chemical, were dissolved in the urea-water solution, withagitation and heating to 140F. The resulting solution was added slowlywith agitation to parts by weight ofpolyhydroxypolyalkylenepolyureaformaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. content of approximately 30%. Theresulting solution was agitated for 10 minutes and 2.5 parts by weightof 75% Phosphoric Acid catalyst were slowly added. After an additional 5minutes of mixing, 0.4 parts by weight of surfactant Igepal CO 630,General Aniline, were slowly added.

The fluid had the following properties: pH 6.8, stability 20 days.

. The fluid was applied by a hand-operated simulated rotogravure methodon soft, absorbent two-ply dry crepe paper, i.e., facial tissue. Theyellow imprinted area had a transfer rating of 3 after 4 weeks of aging.

EXAMPLE 34 3.92 parts by weight of an acid dye, Lanasyn Brilliant BlueGL, C.I. Aicd Blue 127, Sandoz, and 0.08 parts by weight-of a directdye, Erie Brilliant Violet B Conc. (200%), C1. Direct Violet 9, AlliedChemical, and 0.08 part by weight of a direct dye, Pontamine Black ETP,C.I Direct Black 38, were dissolved in water, with agitation and heatingto F. The resulting solution was added slowly with agitation to 100parts by weight of polyhydroxypolyalkylenepolyurea-formaldehydecondensate (Uformite 700, Rohm & Haas) having an N.V.S. content ofapproximately 30%. The resulting solution was agitatedfor minutes and 4parts by weight of Ammonium Chloride catalyst were slowly added.

The fluid had the following properties: pH 5.5, viscosity 3.70 cps,stability days. i

The fluid was applied by hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 0 after 4 weeks of aging.

EXAMPLE 35 10 parts by weight of urea were added to 90 parts of water ina container equipped with an agitator and means for heating. 4 parts byweight of a reactive dye, Primazin Green GL, BASF, were dissolved in theureawater solution, with agitation and heating to 100F. The resultingsolution was added slowly with agitation to 100 parts by weight ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (Uformite 700,Rohm & Haas) having an N.V.S. content of approximately 30%. Theresulting solution was agitated for 10 minutes and 2.50 parts by weightof 75% Phosphoric Acid catalyst were slowly added. After an additional 5minutes of mixing, 0.4 part by weight of surfactant lgepal CO 630,General Aniline, was slowly added.

The fliud had the following properties: pH 6.7, stability 37 days, gel.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The greenimprinted area had a transfer rating of 2 after 4 weeks of aging.

' EXAMPLE 36 6 parts by weight of urea were added to 94 parts of waterin a container equipped with an agitator and means for heating. 4.partsby weight of an acid dye, Berkshire Phloxine G. Conc. (150%), CI. AcidRed '1, were dissolved in the urea-water solution, with agitation andheating to 140F. The resulting solution was added slowly with agitationto 100 parts by weight of polyhydroxypolyalkylenepolyurea-formaldehydecondensate (Uformite 700, Rohm & Haas) having an N.V.S. content ofapproximately 30%. The resulting solution was agitated for 5 minutes and1.76 parts by weight of 75% Phosphoric Acid catalyst were slowly added.After an additional 5 minutes of mixing, 0.4 part by weight ofsurfactant lgepal CO 630, General Aniline, were slowly added.

The fluid had the following properties: pH 7.1, stability 21 days. I

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 0 after 4 weeks of aging.

EXAMPLE 37 3.08 parts by weight of a reactive dye, Cibacron Yel- EXAMPLE38 parts by weight of resin polyhydroxypolyalkylenepolyurea-formaldehydecondensate (Uformite 700, Rohm &'Haas) 30% N.V.S., were modified byaddition of 90 parts by weight of water, 30 parts by weight of urea,1.76 parts by weight of 75% Phosphoric Acid and mixed unitl solution washomogeneous.

3.88 parts by weight of a reactive dye, Drimarine Scarlet Z-GL P.A.F.,C.1. Reactive Red 19, Sandoz, 0.12 part by weight of a reactive dye,Drimarine Red Z-2B P.A.F., C.I. Reactive Red 17, Sandoz, were addeddirectly to the modified resin solution described above with agitationand heating to F. The dye-resin was mixed until solution was complete.Then 0.4 parts by weight of surfactant lgepal CO 630, General Anilinewas added, slowly.

The fluid had the following properties: pH 6.8, N.V.S. 22.7%, specificgravity 1.102, viscosity 3.69 cps, surface tension 33.3 dyne s/cm.

The fluid was applied by a hand-operated simulated rotogravure method onsoft-absorbent two-ply crepe paper, i.e., facial tissue. The pinkimprinted area had a transfer rating of 1 after 4 weeks of aging.

EXAMPLE 39 weight of surfactant lgepal CO 630, General Aniline,

was added, slowly.

The fluid had the following properties: pH 6.75,

N.V.S. 23.2%, specific gravity 1.106, viscosity 3.55

cps, surface tension 32.9 dynes/cm.

The fluid was applied by hand-operated simulated rotogravure method onsoft, absorbent two-ply crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 0 after 4 weeks of aging.

EXAMPLE 40 100 parts by weight of resinpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (Uformite 700,Rohm & Haas) 30% N.V.S., were modified by addition of 90 parts by weightof water, 30 parts by weight of urea, 1.76 parts by weight of 75%Phosphoric Acid and mixed until the solution was homogeneous.

4 parts by weight of an acid dye, Brilliant Acid Blue G2L, Geigy, wereadded directly to the modified resin solution described above withagitation and heating to F. The dye-resin was mixed until solution wascom weight of'a direct dye, Pontarriine Fast Yelplete. Then 04 part byweight of surfactant lgepal CO 630, General Aniline, was added, slowly.

The fluid had the following properties: pH 7.0,

- N.V.S. 23.2%, specific gravity-1.100, viscosity 4.08

cps, surface tension 33.0 dynes/cm.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of after 4 weeks of aging.

EXAMPLE 41 100 parts by weight of resinpolyhydroxypolyalkylenepolyurea-formaldehyde condensate dition of 90parts by weight of water, parts by weight of urea and 25 parts by weightof 75% Phosphoric Acid and mixed until solution was homogeneous.

6'parts by weight of a direct dye, Pontamine Fast Yellow RL, C.l. DirectYellow 50, DuPont, were added directly to the modified resin solutiondescribed above with agitation and heating to 140F. The dye-resin wasmixed until solution was complete. Then 0.4 part by weight of surfactantlgepal CO 630, General Aniline, were added, slowly.

The fluid had the following properties: pH 6.85, N.V.S. -.23.8%,specific gravity 1.108, viscosity 4.04 cps, surface tension 33.3dynes/cm.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent two-ply crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 1 after 4 weeks of aging.

What is claimed is:

l. A low-viscosity printing fluid suitable for printing cellulose webswhich comprises an aqueous solution of a watersoluble, cationic,thermosetting, polyhydroxypolyalkylenepolyurea-formaldehyde resincondensate and a water-so1uble dye compatible with said resin, said dyeand resin mixture having a stability of from about 1 hour to in excessof 4 months and a transference value of from about 0 to about 4, and aviscosity of less than cps at 77F.

2. A low-viscosity printing fluid as claimed in claim 1 wherein theresin is a water-soluble, cationic, thermosettingpolyhydroxypolyalkylenepolyureaformaldehyde resin condensate prepared bya process which comprises reacting between about 0 and 100C., in thepresence of water, epichlorophydrin and an alkylene polyamine having twoto three carbon atoms in the alkylene portion thereof in a mole ratiofrom 1:1 to 1.4:1 until an aqueous solution of the resultingpolyhydroxypolyalkylenepolyamine at a concentration of about 46% has aviscosity from J to'Z, at C. on the Gardner-Holdt scale; reacting saidpolyhydroxypolyalkylenepolyamine with urea between 100 and 200C. in aratio from 0.5:1 to 1.811 of urea per Nl-lgroup of saidpolyhydroxypolyalkylenepolyamine until an aqueous 45% solution of theresulting polyhydroxypolyalkylenepolyurea has a viscosity from B to Z at25C. on the Gardner-Holdt scale; and reacting saidpolyhydroxypolyalkylenepolyurea with formaldehyde in a solution at a pHbetween 7 and 9.5.

3. A low-viscosity printing fluid as claimed in claim 2 which isfree'from tinctorial particulate matter and which has a viscosity ofless than 15 cps at 77F., a stability of from about 1 hour to in excessof 4-months,

and a transference value of from about 0 to about 4 as (Uformite 700,Rohm & Haas) N.V.S., were modified by admeasured against standardizedsolutions of a standard thermosetting resin and a standard dye.

4. A low-viscosity printing fluid as claimed in claim 3 which has atransference value of from 0 to '2.

5. A low-viscosity printing fluid as claimed in claim 1 wherein theresin is a water-soluble, cationic, thermosettingpolyhydroxypolyalkylenepolyureaformaldehyde resin condensate prepared bya process which comprises reacting between about 0 and 100C, in thepresence of an inert volatile solvent, epichlorohydrin and an alkylenepolyamine having two to three carbon atoms in the alkylene portionthereof in a mole ratio of 1:1 to 1.421 yielding soluble reactionproducts, continuing this reaction until an aqueous solution of theresulting polyhydroxypolyalkylenepolyamine hydrochloride at a polyamineconcentration of about 46% has a viscosity of J to 2 at 25C. on theGardner-l-loldt scale, neutralizing the hydrochloride portion thereof,reacting the polyhydroxypolyalkylenepolyamine with urea between 100 and200C. with evolution of'ammonia, the ratio of moles of urea per NH groupof said polyhydroxypolyalkylenepolyamine being from 0.5:1 to 1.821,continuing this reaction until an aqueous 45% solution of the resultingpolyhydroxypolyalkylenepolyurea has a Gardner-Holdt viscosity at 25C. ofB to Z and reacting said polyhydroxypolyalkylenepolyurea with 0.5 to 3moles of formaldehyde per NH group of saidpolyhydroxypolyalkylenepolyurea.

6. A low-viscosity printing fluid as claimed in claim 4 which is freefrom pigmented particulate matter and which has a viscosity of less than15 cps at 77F., a stability of from about one week to in excess of fourmonths, and a transference value of from about 0 to about 3 as measuredagainst standardized solutions of a standard thermosettingresin and astandard dye.

7. A low-viscosity printing fluid as claimedin claim 1 wherein the resinis a water-soluble, cationic, thermosettingpolyhydroxypolyalkylenepolyureaformaldehyde resin condensate prepared byaprocess which comprises reacting between about 0 and 100C. in thepresence of water epichlorohydrin and a polyethylenepolyamine in a moleratio from 1:1 to 1.4:1 yielding solublepolyhydroxypolyalkylenepolyamines, continuing this reaction until anaqueous solution of the resulting polyhydroxypolyalkylenepolyaminehydrochloride at a polyamine content of about 46% has a viscosity from Tto 2., at 25C. on the Gardner-Holdt scale, neutralizing thehydrochloride portion thereof, reacting thepolyhydroxypolyalkylenepolyamine with urea between 100 and 200C. withevolution of ammonia until an aqueous solution containing about 45% ofthe resulting polyhydroxypolyalkylenepolyurea has a Gardner-l-loldtviscosity at 25C. of F to Z, the ratio of .urea to -Nl-l group of saidpolyhydroxypolyalkylenepolyamine in the reaction mixture being between0.5:1 and 1.811, and reacting in aqueous solution at a pH between 7 and9.5 formaldehyde and said polyhydroxypolyalkylenepolyurea in a ratio of1 to 2 moles of formaldehyde per -Nl-l group of said polyurea.

8. A low-viscosity printing fluid as claimed in claim 7 which issubstantially free from volatile solvents having a vapor pressure lessthan that of water and'which has a stability of from about one week toin excess of four months, a transference value of from about 0 to about2 as measured against standardized solutions of a standard thermosettingresin and a standard dye, a viscosity in the range of from about 3.0 cpsto about 7.0 cps, and a surface tension of from about 30 dynes/cm. toabout dynes per centimeter.

9. A fibrous web product having a permanent print thereon which isderived from a fluid as claimed in claim 1.

2. A low-viscosity printing fluid as claimed in claim 1 wherein theresin is a water-soluble, cationic, thermosettingpolyhydroxypolyalkylenepolyurea-formaldehyde resin condensate preparedby a process which comprises reacting between about 0* and 100*C., inthe presence of water, epichlorophydrin and an alkylene polyamine havingtwo to three carbon atoms in the alkylene portion thereof in a moleratio from 1:1 to 1.4:1 until an aqueous solution of the resultingpolyhydroxypolyalkylenepolyamine at a concentration of about 46% has aviscosity from J to Z, at 25*C. on the Gardner-Holdt scale; reactingsaid polyhydroxypolyalkylenepolyamine with urea between 100* and 200*C.in a ratio from 0.5:1 to 1.8:1 of urea per -NH-group of saidpolyhydroxypolyalkylenepolyamine until an aqueous 45% solution of theresulting polyhydroxypolyalkylenepolyurea has a viscosity from B to Z3at 25*C. on the Gardner-Holdt scale; and reacting saidpolyhydroxypolyalkylenepolyurea with formaldehyde in a solution at a pHbetween 7 and 9.5.
 3. A low-viscosity printing fluid as claimed in claim2 which is free from tinetorial particulate matter and which has aviscosity of less than 15 cps at 77*F., a stability of from about 1 hourto in excess of 4 months, and a transference value of from about 0 toabout 4 as measured against standardized solutions of a standardthermosetting resin and a standard dye.
 4. A low-viscosity printingfluid as claimed in claim 3 which has a transference value of from 0 to2.
 5. A low-viscosity printing fluid as claimed in claim 1 wherein theresin is a water-soluble, cationic, thermosettingpolyhydroxypolyalkylenepolyurea-formaldehyde resin condensate preparedby a process which comprises reacting between about 0* and 100*C., inthe presence of an inert volatile solvent, epichlorohydrin and analkylene polyamine having two to three carbon atoms in the alkyleneportion thereof in a mole ratio of 1:1 to 1.4:1 yielding solublereaction products, continuing this reaction until an aqueous solution ofthe resulting polyhydroxypolyalkylenepolyamine hydrochloride at apolyamine concentration of about 46% has a viscosity of J to Z7 at 25*C.on the Gardner-Holdt scale, neutralizing the hydrochloride portionthereof, reacting the polyhydroxypolyalkylenepolyamine with urea between100* and 200*C. with evolution of ammonia, the ratio of moles of ureaper -NH- group of said polyhydroxypolyalkylenepolyamine being from 0.5:1to 1.8:1, continuing this reaction until an aqueous 45% solution of theresulting polyhydroxypolyalkylenepolyurea has a Gardner-Holdt viscosityat 25*C. of B to Z3, and reacting said polyhydroxypolyalkylenepolyureawith 0.5 to 3 moles of formaldehyde per -NH- group of saidpolyhydroxypolyalkylenepolyurea.
 6. A low-viscosity printing fluid asclaimed in claim 4 which is free from pigmented particulate matter andwhich has a viscosity of less than 15 cps at 77*F., a stability of fromabout one week to in excess of four months, and a transference value offrom about 0 to about 3 as measured against standardized solutions of astandard thermosetting resin and a standard dye.
 7. A low-viscosityprinting fluid as claimed in claim 1 wherein the resin is awater-soluble, cationic, thermosettingpolyhydroxypolyalkylenepolyurea-formaldehyde resin condensate preparedby a process which comprises reacting between about 0* and 100*C. in thepresence of water epichlorohydrin and a polyethylenepolyamine in a moleratio from 1:1 to 1.4:1 yielding solublepolyhydroxypolyalkylenepolyamines, continuing this reaction until anaqueous solution of the resulting polyhydroxypolyalkylenepolyaminehydrochloride at a polyamine content of about 46% has a viscosity from Tto Z4 at 25*C. on the Gardner-Holdt scale, neutralizing thehydrochloride portion thereof, reacting thepolyhydroxypolyalkylenepolyamine with urea between 100* and 200*C. withevolution of ammonia until an aqueous solution containing about 45% ofthe resulting polyhydroxypolyalkylenepolyurea has a Gardner-Holdtviscosity at 25*C. of F to Z, the ratio of urea to -NH- group of saidpolyhydroxypolyalkylenepolyamine in the reaction mixture being between0.5:1 and 1.8:1, and reacting in aqueous solution at a pH between 7 and9.5 formaldehyde and said polyhydroxypolyalkylenepolyurea in a ratio of1 to 2 moles of formaldehyde per -NH- group of said polyurea.
 8. Alow-viscosity printing fluid as claimed in claim 7 which issubstantially free from volatile solvents having a vapor pressure lessthan that of water and which has a stability of from about one week toin excess of four months, a transference value of from about 0 to about2 as measured against atandardized solutions of a standard thermosettingresin and a standard dye, a viscosity in the range of from about 3.0 cpsto about 7.0 cps, and a surface tension of from about 30 dynes/cm. toabout 60 dynes per centimeter.
 9. A fibrous web product having apermanent print thereon which is derived from a fluid as claimed inclaim 1.